Al-Nahrain Journal of Science

ANJS, Vol.24 (3), September, 2021, pp. 9-15

Chemistry of Some Organotin Compounds

Hassan Ghani and Emad Yousif*
Department of Chemistry, College of Science, Al-Nahrain University, Baghdad, Iraq

Article’s Information Abstract

Organotin compounds (OTCs) are characterized as having at minimum one

Received:
covalent bond between carbon and tin atoms, and are usually denoted by the
24.08.2021
Accepted: formula RnSnX4-n (n = 1-3, R = aryl or alkyl, X = halogen ion or a carboxylate,
04.09.2021 etc.). There are several methods to synthesis organotin compounds, they are
Published: Grignard and Kocheshkov reactions, Wurtz reaction and alkylation method. The
tin has two stable state, (II) and (IV). Sn (II) forms pyramidal sp3 complexes as
30.09.2021
well as trigonal bipyramidal sp3d complexes, whereas Sn (IV) forms trigonal
bipyramidal sp3d complexes or octahedral sp3d2 complexes.
Keywords:
OTCs alkylation method
Kocheshkov reaction

DOI: 10.22401/ANJS.24.3.02
*Corresponding author: emad_yousif@hotmail.com

1. Introduction
Organotin compounds (OTCs) are characterized as having
at minimum one covalent bond between carbon and tin
atoms, and are usually denoted by the formula RnSnX4-n (n
= 1-3, R = aryl or alkyl, X = halogen ion or a carboxylate,
etc.), [1]. The tin electronic configuration is 5s25p2 and has
two stable states of oxidation, i.e.; IV and II. Organotin (II)
compounds are readily oxidized to more stable organotin
(IV) compounds. Organotin compounds classified by the
number of organic groups as mono, di, tri and tetraorganotin
(IV) according on the number of groups of aryl (Ar) or alkyl
(R) attached to them [2]. Organotin compounds are also
classified into aromatic and aliphatic organotins [3].
The history of organotin is extensive, starting in 1849,
where Frankland isolated a sample of diethyltin diiodide Figure 1. Some organotin (IV) compounds.
[4]. Lowich in 1852, he showed how alkyl halides react with
a tin-sodium alloy to form tin-alkyl compounds [5]. The 2. Existence of Organotin Compounds
preparation of tetra alkyl and tetra arylstannanes from Organotin compounds, commonly known as stannes, are
Grignard reagents and alkyltin halides or tin tetrachloride, tin-based chemical compounds containing hydrocarbon
was describe in 1903 by Pope and Peachey and this method substituents that were discovered in nature. Organotin
became the norm for synthesizing organotin compounds [6]. chemistry is a branch of organometallic chemistry that deals
with the chemistry of tin. An organotin compound is
employed as a biocide, a hydrochloric acid scavenger, and
a heat stabilizer in polyvinylchloride (PVC). Trityltin oxide
has been used as a wood preservative for many years.
Antifouling agents containing butyltin are utilized in the
maritime environment. The International Maritime
Organization (IMO) has imposed a worldwide ban on the
use of these compounds due to concerns about their toxicity.
Butyltin trichloride is used to make glass bottles or tin oxide
layers by vapor deposition [3].

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ANJS, Vol.24 (3), September, 2021, pp. 9-15

3. Organotin Compound Classification substituents for stability. Reich discovered and

Organotin compounds are divided into four types: mono, characterized lithium pentaorganostannates in solution for
di, tri, tera organotins. the first time in 1986. The following year, a six-coordinated
Mono-organotin compounds: RSnX3 are well-known, tetraorganotin compound was discovered. A crystal
although its application is limited. Butyltin sulfide is a structure of all carbon pentaorganostannane that is stable at
polyvinylchloride stabilizer [3]. ambient temperature was described in 2007 [8]. Figure 2
Di-organotin compounds: R2SnX3 is highly reactive, shows the distribution of tin production by region in 2008.
and this property is central to the majority of their
applications. s. They are used as PVC stabilizers,
polyurethane foam catalysts, and silicon elastomer cold-
curing catalysts [7].
Tri-organotin compounds: The most significant class
of organotin chemicals are R3SnX. They have a high
biological activity and are commonly used as biocides. The
chemical nature of the R group has a strong influence on the
biological properties of these compounds [3].
Tetra-alkyl and tetra-aryltin: The majority of these
compounds are employed as intermediates in the production
of other organotin compounds. Tetra-alkyltin compounds
are colorless and liquid at room temperature. Tetra-
organotin compounds are soluble in the presence of air and Figure 2. World production of tin [9].
water and have typical covalent bonds. Sn(C4H9)4 Tetra-
butyltin is a colorless, oily liquid with a distinctive odor. 4. Overview Synthesis
Tetra-phenyltin Sn(C6H5)4 is a white crystalline powder The alkylation of Sn with organo-aluminum or magnesium
which is soluble in organic solvents but it does not dissolve compounds is the most common way to make organotin
in water. Estertins are a new class of organotin chemicals compounds. Grignard reagents are made from metal and
that have been developed for usage as poly (vinyl chloride) aryl or alkyl halides and require a great deal of solvent and
stabilizers since 1974. Their general structure is are extremely costly. It is hard to stop the partial alkylation
(R−O−CO−CH2CH2)2SnX2 or R−O−CO−CH2−CH2SnX3, reaction with SnCl4 unless R is very large, therefore the
where X is isooctylmercaptoacetate. They're simple to reaction is usually completed to produce R4Sn.
extract and have a low level of volatility [7].
RX+Mg RMgX (1)
Hypercoordinated stannanes: Tin compounds, unlike
4RMgX +SnCl4 R4Sn +4MgXCl (2)
their carbon counterparts, can have five or even six atoms
Redistribution occurs when tetra-alkylestanane is heated
coordinated instead of the normal four these hyper
with the right amount of SnCl4, resulting in alkylene
coordinated compounds often feature electronegative
chloride (RnSnCl4-n), Scheme 1.

Scheme 1. Organotin synthesis based on the Grignard and Kocheshkov reactions.

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ANJS, Vol.24 (3), September, 2021, pp. 9-15
In Wurtz reaction, tetra-butyltin was synthesized from
tin tetra-chloride by adding a mixture of butyl chloride and
stannic chloride to the boiling sodium solution as shown in
the stoichiometry chemical reaction equation [10].
4BuCl+SnCl4 + 8Na ⎯→ Bu4Sn + 8NaCl (3)
This process was carried out in accordance with Wurtz's
reaction, created by Ladenburg in 1871, who prepared
phenyltriethyltin by "refluxing an ethereal solution of
triethyltin iodide and bromobenzene with sodium".
Alkylation of tin (IV) halides with an organometallic
reagent that includes metals such as aluminium or lithium
[11].
4R3Al + 3SnCl4 ⎯→ 3R4Sn + 4AlCl3 (4)
2RLi + SnCl4⎯→ R2SnCl2 + 2LiCl (5)
5. Overview of Structures
Sn (IV) and Sn (II) are both stable states. The unshared
single pair in the Sn (II) state is predominantly in the 5s
state, with a small p. The 1, stannylenes SnX2 molecules
have a XSnX angle of approximately 90-100°. When there
are significantly electron-attracting ligands, these
compounds have been the most stable, causing the loss of
the residual electron pair very difficult for example (SnF 2
and SnCl2). Otherwise, in the case of Sn (IV), where tin is
sp3 hybridized and the SnX4 (4, stannane) molecule
possesses tetrahedral symmetry.
Both stannanes and stannylenes, however, have
unoccupied 5d orbitals that can receive one or more
additional ligands. Stannylenes easily form pyramidal sp 3
and trigonal bipyramidal sp3d complexes [SnX3 (2), SnX4
(3) respectively], while stannanes readily form trigonal
bipyramidal sp3d or octahedral sp3d2 complexes [SnX5 (5),
SnX6 (6) respectively] [12].
Figure 3. Proposed structure of organotin compounds.
6. Thermal Properties
The majority of organotin products have excellent long-
term stability at room temperature and are as solids. It
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begins to deteriorate when heated above 100 °C, so it can
be safely heated to 50 °C. [16]. Organotin polymers usually
degrade without melting. Hundreds of degrees are
frequently attained, with little or no weight loss [16,17].
Organotin Compound Physical and Chemical
Properties
All the compounds of organotin are cations. They are
preserved in equilibrium by inorganic or organic anionic
ligands in nature and in industrial chemicals. The vast
majority of industrial organotin chemicals are made up of
an organotin cation and one or maybe more ligands. The
hydrophobicity of organotin increases as the number of
alkyl groups and the length of the alkyl chain increases
[13,14].
The organotin compounds have low solubility in water
depending on concentration of the temperature, suspended
particles and pH. Organotin compounds have a very high
affinity for fats and organic solvents [15].
7. Environmental Chemistry of Tin
Organometallic tin has higher toxicity compounds than
inorganic tin and there is a great deal of importance for
biomethylation of tin. The methylation of tin by
methylcobalamin (CH3−B12) demands a one electron
oxidation of Sn (II) to a Sn (III) radical, which can occur in
the presence of Fe (III). Sn (IV) would, of course,
necessitate a single electron reduction. The stannyl radical
Sn (III) can then combine with Co (III) to form CH3-SnCl2,
lowering cobalamin levels [3].
8. Applications of Organotin Compounds
The first organotin compounds were synthesized in 1852,
and after 80 years of synthesis, organotannans were used as
transformers for vinyl plastics and transformer oils. The
commercial use of organotin compounds rapidly increased
as a result of the growth and the interest of Van Der Keek
and colleagues in the 1950s [18]. The applications of tin in
2008 are shown in Figure 4.
Figure 4. Applications of tin [9].
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9. PVC Stabilization
One of the most common commercial polymers is poly
(vinyl chloride), with third-largest output behind
polyethylene and polypropylene. It is utilized in a variety of
applications, including construction, food and blood bags,
home decor, and wire coating.
PVC suffers from low stability in thermal and light
environments. On exposure to heat and light, it undergoes
fast autocatalytic dehydro-chlorination through its molding
and use [19,20] Consequently, from the beginning of the
reaction, conjugated polyene sequences are formed, giving
rise to polymer discoloration and seriously changing its
physical properties [21].
Since 1940, organotin compounds have been utilized as Figure 7. Diorganotin(IV) complexes with benzamido-
plastic stabilizers to delay degradation. Dibutyltin methyl leucine [24].
maleate, dibutyltin dilaurate, and dibutyltin maleate were
the first commercially effective stabilizers. The stabilizer is The efficiency of photostabilizing of PVC was studied
typically loaded at 0.5-2% by weight of the polymer [22]. in the existence of organotin (IV) complexes as
The effect of diorganotin (IV) complexes (Bu2SnL2, photostabilizer, Ph3SnL, Me2SnL2 and Bu2SnL2 with
Me2SnL2 and Ph2SnL2) with benzami-doacetic acid as furosemide as ligand, Figure 7 were synthesized and
ligand was studied as photostabilizers of PVC, Figure 5. By characterized and used as additives to enhance the
HCl scavenging, radical scavenger, peroxide decomposer photostability of PVC after irradiation. [25].
and UV absorption processes, these additives stabilize PVC
film [23].

Figure 5. Diorganotin (IV) complex [23].

The effect of diorganotin(IV) complexes (Bu2SnL2,
Me2SnL2 and Ph2SnL2) with benzamidoleucine as ligand
was studied as PVC photostabilizers, complexes structure
shown in the Figure 6. The photostabilization of PVC in the
existence of organotin(IV) complex take the form:
Bu2SnL2 < Me2SnL2 < Ph2SnL2, [24].

Figure 7. Di and Triorganotin (IV) complexes with

furosemide [25].
Three diorganotin (IV) complexes (Ph2SnL2, Me2SnL2
and Bu2SnL2) using naproxen as ligand, Figure 8 were
studied as photo-stabilizers additive to inhibit the photo-
degradation of PVC. The organotin (IV) complexes act as
photostabilization for PVC and Me2SnL2 was the most
effective photostabilizer [26].

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Figure 8. Diorganotin (IV) complexes (Ph2SnL2, Me2SnL2
and Bu2SnL2) containing Naproxen.
10.Biological Activities
The general biological activities of microorganisms of
organotin compounds have been studied since the fifties. To
insects, mammals, fungi, and bacteria, inorganic tin
compounds are non-toxic or only moderately toxic, whereas
organotin compounds display a broad range of biological
effects. The toxicity of alkylorganostannanes depends to a
large extent on the alkyl group, whereas the number of alkyl
groups decreases the activity decreases as follows for IV tin
compounds:
R4Sn > R3Sn > R2Sn > Rsn > Sn
with little effect of the anionic group X on the activity [16].
Recently organic tin compounds have been tested
against human lung cancer cells (A549). Two novel
organotin (IV) complexes were synthesized, characterized
and it has proven effective in the field of lung cancer figure
(9) [27].
Figure 9. Structure of di-organotin (IV) complexes.
11.Agents of Antifouling
Organotin (IV) compounds, especially tributyltin have
been used to coat ship hulls to protect them from attack by
microorganisms. Because of the increased weight and
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roughness of the hull, the ship consumes more fuel, requires
more frequent dry docking, and incurs higher cleaning costs
[28].
Figure 10. Structure of tributyltin (TBT).
12.Glass Coating
Organotin (IV) halides are used to generate thin electrical
conductive films on surface of glass by use atmospheric
pressure chemical vapor deposition (AP-CVD) procedures
due to their low cost and many commercial applications
[29,30]. Tin chloride is a precursor to transparent
conductive oxide (TCO) films [31].
SnCl4 + 2H2O → SnO2 + 4HCl
13.Wood Protection
Various woods have been successfully preserved against
bacteria, fungi, insects and. wood boring marine. animals in
trials. Tri-butyltin complexes possess good antimicrobial
activity and can be utilized in wood preservation. One of the
most significant characteristics of Organotin (IV)
compounds is that. they. not impart. odor or coluor to treated
wood. In a vacuum, wood is treated with organotin (IV)
compounds, and the results are released in a flow of
organotin (IV) which is already attached to the cellulose's
terminal OH groups to protect it from microbial destruction
[22].
In this connection new organotin biocides namely are of
interest due to their increased resistance to UV
radiation[32], Figure 11.
Figure 11. 1-stan- 3,5-disil-4-oxacyclohexane.
14.Conclusion
Organotin compounds have a large number of industrial and
technological applications. These applications are PVC
polymer stability, various biological activities, wood
 Al-Nahrain Journal of Science
ANJS, Vol.24 (3), September, 2021, pp. 9-15
protection and antifouling agents. As we discussed in our
review of the use of organotin (IV) as photo-stabilizers of
PVC materials, many significant results have been obtained.
Organic tin compounds have been tested against human
lung cancer cells (A549). Recently, organic tin (IV)
complexes have been used in the field of lung cancer and
have proven effective in the treatment of lung cancer.
Acknowledgments
This project is supported by Al-Nahrain University.
Conflicts of Interest
The authors declare no conflict of interest.
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